Milk soluble alginate compound and process



Patented Get. 26, 1937 UNITED STATES MILK SOLUBLE COMPOUND AND Howard J.Lucas, Pasadena, cum, lllfllfl! to Kelco Company, Loo Angelou, can, acorporation of Delaware No Drawing.

Application July 2, 1934, Serial No. 733,530. Renewed June 3, 1937 34Claims.

This invention is a new alginate compound an process of producing same.v

The object of the invention is'to produce an alginate compound which isreadily soluble in milk for use in connection with dairy products.

A further object "of the invention is to produce a readily solublealginate compound useful in the industrial arts. 1

All alginates heretofore made, to the best of my knowledge andinformation, have T n insoluble in milk or products containing milk.This is especially true or the high viscosity alginates, even when mixedwith a fairly large percentage of sugar and dried. Heretofore suchalginates, or mixturesthereoi, although finely ground will notcompletely dissolve when added to milk, at

room temperature, at 180 F., orat intermediate temperatures, but thealginates remain suspended in the form. of distinctly visible particleseven after long and vigorous stirring. Consequently when such alginateswere used in dairy products, it was necessary to first prepare a watersolution of the alginate and add this to the milk. Thus in usingalginates in chocolate milk drinks the alginate had to be firstdissolved in water, then cocoa added, and then the other ingredientssuch as sugar, malt, flavoring, etc., to make a syrup, and then add suchsyrup to the milk in the proportions desired. Also when alginates wereto be used in ice creams, the alginate had to be first dissolved inwater and then added to the ice cream mix. Some manufacturers of icecream object to any addition of water to their mixture and therefore,cannot use alginate in their ice cream. Similarly, heretofore alginatesfor use in buttermilk and other dairy products had to be first dissolvedin water. The necessity for first making water solutions of thealginates not only involved expense and time in preparing the finaldrink or edible, but in some cases the water affected the quality; andspecial equipment was involved and many dairies lacking such equipmenthave been unable to use alginates for the above reasons.

My novel product more specifically consists of a relatively dry solublealginate compound which may be dissolved directly in milk, or productscontaining milk, without preliminary dissolving in water or specialhandling such as heretofore required; and without any special equipment;and solutions of my novel product in milk can be made in the usualpasteurizing vats.

One practical method of manufacturing my novel milk soluble alginatecompound is as follows: A quantity of alginic acid (preferably such asdisclosed in Thornley-Walsh Patent No. 1,814,- 981, July 14, 1931; andClark-Green application Serial No. 693,891, filed October 16, 1933, and.Green application Serial No. 721,829, filed April 21, 1934, whichusually contains about 85% to 5- 90% water and has a fibrous character)is placed in a suitable mixer.

Enough soda ash is then added to the alginic acid to produce, whenthoroughly mixed there= with, a sodium alginate paste-oi about 7 pH. 10Preferably the soda ash is dusted into the mixer to aid in uniformlydistributing it throughout the mass. In place of soda ash otherneutralizing" agents, such as sodium bicarbonate and sodium hydroxide beused. The mixing is continued long enough (usually. about minutes) tninsure conversion of all the alginic acid into a sodium alginate paste.

To this paste is then added a phosphate (preferably trisodium phosphate)or similar material. The anhydrous weight or such trisodium phosphate isapproximately equal to A, of the anhydrous weight of the alginic acid.This trisodium phosphate is added in form (NaaPOalZl-IzO or NaaPOaHziO)and mixed intothe to until it has thoroughly dissolved and reacted; thisordinarily occurs in about ten minutes time. n milk powder or othersuitable agent is employed, it is added in a similar 21:21.: tthephgsphg'te, When sugar, or other suitable agent for increasingsolubility and for controlling the colloidal emciency of the product, isit is addedin a similar manner to the phosphate. 35

The resultant mixture is then spread onto trays and dried. If dried inthe sun one to three days time is required depeg on the weatherconditions. It may be dried cially by means of a drum dryer, spraydryer, mechanical tray belt tunnel dryer, or other suitable means. Insome cases it has been found desirable to add milk powder to thismixture to assist in drying during the manufacture of the dry solublecompound. The additicn of milk powder or other suitable agent to themimure before drying greatly assists the". The dried material, which maycontain about 10-15% water is then ground and screened to a convenientsize for marketing. The product may be of any suitable size. Preferablythe dried material is reduced to a size which will pass through a 20meshscreen and over an 80 mesh'screen. The smaller the particle size thefaster the solution rate when the particles are dispersedin ticles (atpresent those which pass through an 80' mesh screen) and place them inthe mixer with the alginic acid and soda ash in the initial step ofpreparing more of my product, this disposes of such fines and they aidin thickening the paste so that it will dry faster.

For a thoroughly milk soluble alginate the pH of the finished product ina 1% water solution would preferably be above 7.5; and ,the more the pHincreases the quicker the product will go into solution in milk.

For practical purposes the minimum ratio of trisodium phosphate(anhydrous) to the anhydrous alginic acid should be about 1:18. whensmaller concentrations are used the product eventually goes intosolution, but not in the normal pasteurizin-g time employed by dairies.

I have found that a mechanical mixture of dry sodium phosphate and drysodium alginate will not give the same result in that it will notdissolve in milk even though such ingredients were first finely groundand intimately mixed together;

and also. that the addition of dry sugar to said mixture will not renderit soluble inmilk.

Chocolate milk drinks may be prepared by adding my novel ,solublealginate compound to the milk in the pasteurizing vat and stirringnormally until it is dissolved, then the desired amount of cocoa andfinally the sugar and other ingredients. After pasteurization iscomplete the drink may be cooled, held and bottled in the usual manner.My novel soluble alginate compound may also be added directly to an icecream mix while stirring it in the pasteurizing vat.

The above described process may be varied as follows and still give amilk soluble alginate compound: Refined alginic acid made by any processmay be used. The salts of the alginic acid may have high orlowviscosity, although agreater suspending power towards cocoa isobtained when a high viscosity alginic acid is used. The acid does nothave to be free of all insoluble alginic acid salts such as calcium oraluminum salts, as such salts will react with thetrlsodium phosphate toform the corresponding insoluble phosphate and soluble sodium alginate.The effectiveness Ofhigh-ash alginic acid is increased by the additionof the trisodium phosphate.

A soluble alginate such as ammonium, potassium or magnesium alsinate, orany other suitable water soluble alginate, or any combination of these,may be incorporated in a paste form with trisodium phosphate toobtainthe milk soluble phospho-alginate compound. I

When soluble alginates other than sodium alginate are to beincorporated, the corresponding carbonates, bicarbonates or hydroxidesmay be added for neutralizing the alg'inic acid.

In place of trisodium phosphate other phosphates may be used, such asdisodium phosphate, monosodium phosphate, or combinations of these.Phosphoric acid also may be used, or any combination of it with theabove salts. Boluble phosphates other than those of sodium may also beused. Sodium hydroxide or other strong ly basic substance may also beused in conjunction with these compounds in order to bring the pH to thedesired value. In such case the phosphates may be added 'to the alginic.acid before the carbonates. The sodium hydroxide or other strongly basicsubstance may be added previous to, during and/or subsequent to theincorporation of the phosphoric compound with the alginic compound. I

, Ihawalsofoundthatsodiumcaseinandalso milk powder may be used in placeof phosphates. These materials also have the added advantage ofthickening 'the paste and thereby aid in drying. It is probable that themilk powder renders the compound soluble due to the presence of sodiumcaseinate in the milk. The milk powder also increases the solubilityrate of the product similartosugar.

It must be remembered, however, that the ratio of the amount ofsubstitutes used for trisodium phosphate will necessarily have adifierent effective minimum ratio to the alginic acid content than thetrisodium phosphate. The substitution may be complete or partial or madewith several difierent substitutes.

The product may be a sodium phospho-alginate, or as hereinafterdescribed may consist of a compound of sodium alginate and the sodiumsalt of an acid whose calcium salt is insoluble in water, such as sodiumsilicate, sodium citrate, sodium tartrate, sodium carbonate, sodiumcaseinate, according to the specific chemicals employed. In lieu of thesodium compounds mentioned above, the corresponding potassium andammonium salts and other water soluble salts which do not form aprecipitate with sodium alginate may be used. 1

Sodium hydroxide or other strong base may be used when it is desired toregulate or increase the pH of any product.

Instead of using the phosphates, milk powder, sugar, etc., in the dryform they may be mixed with water before incorporating with the alginiccompound.

If desired substances to increase the rate of drying and subsequentsolution, such as sugars,

milk powder, and sodium chloride, may be added creases the effectivenessof the contained sodium alginat'e'in its ability to suspend cocoa. Ihave demonstrated this by the following test: A sodium aiglnate andsugar mixture was made and dried; also a phospho-alsinate was made fromthe same lot of alginic acid. These two products were then-dried, groundand used to'make a I non-settling chocolate milk drink. In the onecontaining phospho-algin'ate 20% less alginate was required to suspendthe cocoa than was required with the sodium alginate-sugar. When achocolate milk was made by suspending cocoa in milk in whichphospho-alginate had previously been added without first dissolving itin water, 27% less alginate was required than in a choco late milk wherethe alginate-sugar mixture was first dissolved in water. Thealginate-sugar mixture could not be testeddirectly in milk as it wouldnot dissolve therein.

My new milk soluble alginate'products substantially increase theeffectiveness of the contained sodium alginate in its ability tostabilize ice cream.

My milk soluble algniate product is'also 'meful to producers of dry milkpowder, as' it can be used by dissolving thedry compound in the milkbefore drying, whether such milk be skim-milk, whole milk, or milk ofany butter fat in between these limits. Mypmduct is also useful indryice ly suspended chocolate milk. All grades of reconstituted milkcontaining my milk soluble product can be used like ordinary grades ofreconstituted milk, or the corresponding grades of fresh milk, as aningredient in an ice cream mix and to such mix it would be unnecessaryto add separately any stabilizer. In the same way dry ice cream mixpowder containing my milk soluble product could he reconstituted inwater, milk or other dairy product to form a complete wet ice cream mixready for freezing to produce ice cream.

M new milk soluble alginate product may a added dry, or in the form of awater solution, to

chocolate liquor or a water solution oi cocoa reconstituted watersolution oi finished cocoa; and these wet mixtures can he dried toproduce a dry non-settling cocoa powder; suchpowder can he added towater and sugar to form a nonsettling syrup which can he added to milkto iorm a non-settling chocolate mills; or such powder can he added tohot milk and sugar to form.

a non-settling chocolate milk without the necescity of first goingthrough the step of making a mp.

Another characteristic by which my new milk soluble product diners fromsodium alginate, or

mixtures of sodium alsinate and sugar, is that it can be mixed withsugar, cocoa, chocolate and flavoring in dry form to produce a compoundwhich when added to hot milk will make a nonsettling chocolate milkdrlnh. Such compound could first he added to water to form a syrup ifdesired, which syrup could he added to hot milh to form a non-settlingdrink. Dry milk-powder oi any butter fat content could he added to theaforesaid compound, and by adding such mixture to water a none-settlingchocolate milk can he produced. So for as i sin advised or can ascertainno sus mndins agent or stabilizer ever before known could he usedm'hereinbeiore described to produce a non-viscous non settling chocolatemilk.

soluble alsinate products are also useful in sunny other industrialarts, and are more eiiec= tire on an-almnate content haste than aleinatesalts alone. and my soluble products are partic= ularly useful iorcreaming latex, and may also used in boiler compounds, automobilepolishes, and emulsifying oils.

I claim:-

i. soluble compound comprising an originate and a water soluble salt ofan acid whose calcium salt is insoluble in water.

A soluble compound comprising an alginate and sodium salts of an acidwhose calcium salt is insoluble in water.

ii soluble phospho-aiginate compound.

d. it. soluble aisinate compound comprising a water soluble salt ofalginic acid and a sodium phosphate.

e. A soluble compound comprising a water soluble salt oi alsinic acidand phosphoric acid.

6. A soluble compound comprising sodium alsinate and sodium salts of anacid whose calcium salt is insoluble in water.

. 7. A soluble phospho-alginate compound having a pH 01' over 7.5.

8. A soluble alsinate compound comprising an alsinate and a salt oi anacid whose calcium salt is insoluble in water, having a pH of over 7.5.

9. A soluble alginate compound comprising a salt of alginic acid andsodium phosphate, and having a pH of over 7.5.

10. A soluble alginate compound comprising a salt of alginic acid andtrisodium phosphate, and having a pH of over 7.5.

11. A soluble alginate compound comprising a soluble salt of alginicacid, a phosphate, and a milk powder.

12. A soluble alginate compound comprising a salt of alginic acid,sodium phosphate, and a milk powder.

13. A dry soluble compound comprising a water soluble salt of alsinicacid, a Water soluble salt of an acid whose calcium salt is insoluble inwater, and a milk powder.

salt is insoluble in. water, and a milk powder.

15. A soluble alginate compound comprising a soluble alginate and aphosphate.

16. A soluble alginate compound comprising a soluble alginate andtrisodium phosphate.

17. A soluble alginate compound comprising a soluble alginate and sodiumcaseinate.

18. A soluble alginate compound comprising a soluble alginate and milkpowder.

19. A soluble aiginate compound, comprising an alginate, a salt oi anacid whose calcium salt is insoluble in water, and sodium hydroxide tocontrol the pH value.

20. The herein described process of producing a milk soluble aiginatecompound; consisting in mixing alginic acid and a neutralizing agentuntil the mass is converted into a paste, then adding sodium salts of anacid whose calcium salt is insoluble in water, and agitating the mixtureuntil it has reacted; drying the mixture; and com minuting the driedmaterial.

2i. ihe herein described process of producing a soluble phospho-alginatecompound, consisting in mixing alginic acid and a neutralizing agentuntil the mass is converted into a paste; then adding a phosphate,agitating the mixture until it has reacted; drying the mixture, andcomminuting the dried material.

22; The herein described process of producing a soluble aiginatecompound, consisting in mixing alginic acid and a neutralizing agentuntil the mass is converted into a paste, then adding caseinate,stirring the mixture until it reacts; drying the mixture; andcomrninuting the dried material.

23, The herein described process of producing a soluble phospho-alginatecompound, consisting in mixing alginic acid and a neutralizing agentuntil the mass is convertedinto a paste, then adding sodium phosphate,and stirring the mixture until it has reacted; drying the mixture; andcom minuting the dried material.

24. The herein described process of producing a soluble alginatecompound, consisting in mixing drying the mixture; and comminuting thedried material. Y

25. The herein described process 01 producing a solublephospho-alginatecompound, consisting in mixing alginic acid and soda ashuntil the mass is converted into sodium alginate, then adding sodiumphosphate, agitating the mixture, drying the mixture, and finallycomminuting the dried material.

26. That step in producing a stabilized milk powder consisting in addingto milk before drying a, milk soluble alginate compound.

27. The herein'described process of producing a soluble alginatecompound, consisting in mixing sodium hydroxide and analginate, adding asalt of an acid whose calcium salt is insoluble in water, drying themixture and comminuting the dry material.

28. The herein described process of producing a soluble alginatecompound, consisting in mixing an alginic acid and a salt of an acidwhose calcium salt is insoluble in water, adding a neutralizing agentand sodium hydroxide to control pI-I, stirring the mixture until it hasreacted, drying the 1 mixture, and comminuting the dry material.

* 29. A soluble alginate product compounded of an alginate, a phosphateand a, strongly basic substance.

30. The method of preparing a soluble alginate compound, consisting inmixing an alginic compound, a phosphoric compound, and a strongly basicsubstance, and drying the mixture.

- 81. The herein described process 01 producing a milk soluble alginatecompound; consisting in mixing alginic acid with a neutralizing agentuntil it has reacted, adding a soluble salt of an acid-whose calciumsalt is insoluble in water, adding a strong base to control the pH,stirring the mixture, drying the mixture and comminuting the drymaterial.

32. The herein described process of producing a milk soluble alginatecompound; consisting in mixing alginic acid with a neutralizing agentuntil it has reacted, adding the soluble salts of acids whose calciumsalts are insolublein water, stirring the mixture, drying the mixtureand comminuting the dry material.

33. The herein described process of producing a milk soluble alginatecompound; consisting in mixing alginic acid and an acid whose calciumsalt is insoluble in water with a neutralizing agent until it hasreacted, drying the mixture and com- HOWARD J. LUCAS.

